EP3899525B1 - Verfahren zur auftrennung und gehaltsbestimmung von stoffen in einer mischung von kohlenwasserstoffen, entsprechende verwendung und vorrichtung - Google Patents

Verfahren zur auftrennung und gehaltsbestimmung von stoffen in einer mischung von kohlenwasserstoffen, entsprechende verwendung und vorrichtung Download PDF

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Publication number
EP3899525B1
EP3899525B1 EP19828249.3A EP19828249A EP3899525B1 EP 3899525 B1 EP3899525 B1 EP 3899525B1 EP 19828249 A EP19828249 A EP 19828249A EP 3899525 B1 EP3899525 B1 EP 3899525B1
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Prior art keywords
supercritical fluid
solvent
use according
compounds
supercritical
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English (en)
French (fr)
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EP3899525A1 (de
Inventor
yang BAI
Stéphanie MOREL
Donia ESSAID
Didier Thiebaut
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville de Paris ESPCI
TotalEnergies Onetech SAS
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Centre National de la Recherche Scientifique CNRS
Ecole Superieure de Physique et Chimie Industrielles de Ville de Paris ESPCI
TotalEnergies Onetech SAS
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/64—Electrical detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/84—Preparation of the fraction to be distributed
    • G01N2030/8447—Nebulising, aerosol formation or ionisation
    • G01N2030/8452—Generation of electrically charged aerosols or ions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels

Definitions

  • the present invention relates to a method for separating and quantifying compounds, in particular polymeric and non-polymeric additives, in a mixture of hydrocarbons.
  • Fuels are mixtures of hydrocarbons resulting from the refining of crude oil.
  • hydrocarbon mixtures particularly for automotive uses in the form of fuel (petrol or diesel)
  • synthetic molecules called additives, are added in small proportions.
  • additives make it possible, for example, to improve the performance of fuels, to pass basic tests, etc.
  • additives can be polymeric or non-polymeric additives.
  • the document WO 2015/112165 A1 presents a method for analyzing hydrocarbon residues from crude oil refining including separation by supercritical phase chromatography.
  • An objective of the present invention is therefore to provide a method for separating and quantifying compounds, in particular additives, for example polymeric or non-polymeric additives, in a mixture of hydrocarbons.
  • Another objective of the present invention is also to provide such a method allowing the separation, quantification and identification of compounds polymers, in particular polymeric additives, in a mixture of hydrocarbons.
  • the present invention relates to the use of a supercritical phase chromatography and CAD detector coupling for the separation and quantification of compounds in a mixture of hydrocarbons.
  • hydrocarbon mixtures may include different compounds, in particular called additives, of any type making it possible in particular to improve the properties of the hydrocarbon mixtures such as, for example, improving performance, in particular maintaining the cleanliness of the engine, in particular by limiting or avoiding the formation of deposits or reducing deposits already present in the internal parts of the combustion engine.
  • additives of any type making it possible in particular to improve the properties of the hydrocarbon mixtures such as, for example, improving performance, in particular maintaining the cleanliness of the engine, in particular by limiting or avoiding the formation of deposits or reducing deposits already present in the internal parts of the combustion engine.
  • These compounds may be polymeric or non-polymeric compounds. We can in particular cite the detergents, carrier oils, cold content boosters, friction modifiers, anti-odors, etc.
  • the method according to the invention makes it possible to separate and quantify all the elements of a hydrocarbon mixture other than the hydrocarbons as such.
  • the method according to the invention is particularly suitable for the separation and quantification of polymers preferably having a molar mass of between 500 and 4000 g/mol, preferably between 1000 and 2000 g/mol.
  • the target polymers according to the invention are polymers comprising a polar hydrophilic head, preferably of small size, for example between 15 and 150 g/mol, preferably between 20 and 60 g/mol, and a non-polar lipophilic hydrocarbon chain.
  • the target polymer may also comprise cycles, for example pyrrolidone.
  • the polar hydrophilic head is preferably an amine function (NH 2 or quaternary amine) or OH (for example sorbitan ester, oleate, glycerol, acid, etc.).
  • the method according to the invention is particularly well suited for target polymers having an amine function, in particular NH 2 , such as for example a group ((CH 2 ) 2 NH) x -(CH 2 ) y -NH 2 in which x is an integer between 1 and 20, preferably between 2 and 10, and y is an integer between 1 and 8, preferably between 2 and 5, or a CH 2 -CH(CH 2 CH 3 )-NH group 2 or OH (e.g. sorbitan ester, oleate, glycerol, acid etc.).
  • NH 2 such as for example a group ((CH 2 ) 2 NH) x -(CH 2 ) y -NH 2 in which x is an integer between 1 and 20, preferably between 2 and 10, and y is an integer between 1 and 8, preferably between 2 and 5, or a CH 2 -CH(CH 2 CH 3 )-NH group 2 or OH (e.g. sorbitan ester, oleate, gly
  • the hydrocarbon mixtures are diesel compositions, in particular B7 diesel.
  • the compounds are polymers other than polyethylene glycols (PEG) and their derivatives.
  • the mobile phase of supercritical phase chromatography is a supercritical fluid comprising CO 2 .
  • the mobile phase can also comprise a co-solvent, for example alcohol, in particular isopropanol or methanol, preferably methanol.
  • the mobile phase comprises 60 to 100% by volume of supercritical CO2 and 0 to 40% by volume of alcohol, for example isopropanol or methanol, preferably methanol.
  • a mobile phase gradient comprising from 2 to 25% by volume of alcohol, for example isopropanol or methanol, preferably methanol and from 98 to 75% by volume of supercritical CO 2 .
  • supercritical CO 2 means a CO 2 fluid maintained at a temperature and a pressure higher than the critical temperatures and pressure of 31.1°C and 7.39.10 6 Pa respectively.
  • the fixed phase (chromatography column) used can be any column known to those skilled in the art.
  • the volume of hydrocarbon mixture injected into the supercritical phase chromatography is between 2 and 10 ⁇ l, preferably between 5 and 8 ⁇ l.
  • the flow rate of the mobile phase is between 0.5 and 1 ml/min, preferably between 0.7 and 0.9 ml/min.
  • the SFC column is at a temperature of approximately 38°C, the pressure is controlled to be approximately 1.24.10 7 Pa.
  • the compounds to be analyzed generally begin to elute from the SFC column from a mobile phase gradient comprising 17% alcohol, preferably MeOH, and a pressure of approximately 3.10 ⁇ 10 7 Pa (SFC system pressure ).
  • Step b) is implemented with a CAD detector, preferably CAD Corona ⁇ .
  • Step b) preferably uses an isocratic solvent.
  • the term isocratic solvent means a solvent whose composition does not change over time, unlike the use of a solvent gradient.
  • the solvent used is a polar solvent or solvent mixture, for example alcohol or acetonitrile, for example methanol or acetonitrile.
  • the isocratic solvent may comprise 5 to 15 mM ammonium formate.
  • the isocratic solvent is preferably mixed to the flow leaving the SFC before entering the CAD.
  • the flow rate of the isocratic solvent is between 0.1 and 1 ml/min, preferably between 0.3 and 0.6 mg/min.
  • the use of an isocratic solvent before the CAD detector makes it possible to have a quantification method applicable to any compound based on a single standard curve.
  • the areas under the peaks are directly proportional to the concentration of compounds in the starting hydrocarbon mixture, whatever the nature of the compound analyzed.
  • this calibration curve can then be used whatever the compound. to analyze.
  • the use of an isocratic solvent according to the invention also makes it possible to overcome baseline problems.
  • the medium is nebulized, for example under a flow of nitrogen, then evaporated to eliminate the mobile phase and the volatile compounds, in particular at a temperature between 30 and 100°C, by example between 50 and 90°C.
  • the particles obtained are positively charged with a flow preferably of nitrogen subjected to a high potential (Corona discharge).
  • An electrometer measures the resulting charged particles, the signal obtained being a function of the analyte concentration.
  • step b) is carried out at a temperature between 30 and 100°C, preferably between 50 and 90°C.
  • the gas pressure during nebulization is between 0.2 MPa and 0.4 MPa.
  • the coupling of supercritical fluid chromatography and the CAD detector makes it possible to considerably reduce the detection limits of compounds in hydrocarbon mixtures, thus making it possible to detect and quantify compounds present in concentrations of up to 100 ppm or even up to 50 ppm.
  • the method of the invention can also include a step of determining the nature of the compound to be analyzed (identification method), for example by mass spectrometry.
  • identity method for example by mass spectrometry.
  • the medium from the supercritical fluid separation column is mixed with the isocratic solvent then injected into a separator.
  • a fraction of the medium is then injected into the mass spectrometer, the other being injected at the CAD detector.
  • the supercritical fluid, the co-solvent, the mixture of hydrocarbons, the isocratic solvent being as defined above.
  • Such a device is described in particular in figure 1 .
  • FIG. 1 There figure 1 is a representation of a device allowing the implementation of the method according to the invention.
  • Example 1 Separation of a polymer 1 in a Diesel B7 mixture
  • Polymer 1 is a polymer comprising a Mannich base polar head.
  • Example 2 Separation of a polymer 2 in a Diesel B7 mixture
  • Polymer 2 is a polyetheramine
  • Example 3 Separation and quantification of polymers 1 and 2 mixed in a Gasole B7 mixture
  • the method according to the invention is implemented on several mixtures of Diesel B7 comprising in a mixture polymers 1 and 2 at concentrations of 0 to 1000 ppm.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Claims (12)

  1. Verfahren zur Auftrennung und Gehaltsbestimmung von Verbindungen, die in einem Kohlenwasserstoffgemisch aus der Rohölraffination enthalten sind, mit den folgenden Schritten:
    a) Auftrennung der im Kohlenwasserstoffgemisch enthaltenen Verbindungen durch überkritische Phasenchromatographie;
    b) Gehaltsbestimmung der einzelnen Verbindungen mit einem Detektor für geladene Aerosole.
  2. Verwendung einer Kopplung aus überkritischer Phasenchromatographie und einem Detektor für geladene Aerosole zur Auftrennung und Gehaltsbestimmung von Verbindungen in einem Kohlenwasserstoffgemisch aus der Rohölraffination.
  3. Verfahren oder Verwendung nach Anspruch 1 oder 2, wobei die Verbindungen Polymere sind, die sich von Polyethylenglykolen (PEG) und deren Derivaten unterscheiden.
  4. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 3, wobei es sich bei den Verbindungen um polymere oder nicht-polymere Verbindungen handelt.
  5. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 4, wobei die mobile Phase der überkritischen Phasenchromatographie ein überkritisches Fluid ist, das CO2 und gegebenenfalls ein Co-Lösungsmittel z. B. Alkohol, insbesondere Isopropanol oder Methanol, vorzugsweise Methanol, umfasst.
  6. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 5, wobei das Volumen des in die überkritische Phasenchromatographie injizierten Kohlenwasserstoffgemisches zwischen 2 und 10 µl, vorzugsweise zwischen 5 und 8 µl, beträgt.
  7. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 6, bei dem die Durchflussrate des überkritischen Fluids zwischen 0,5 und 1 ml/min, vorzugsweise zwischen 0,7 und 0,9 ml/min, liegt.
  8. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 7, wobei in Schritt b) ein isokratisches Lösungsmittel eingesetzt wird, vorzugsweise ein Lösungsmittel, das Methanol oder Acetonitril mit 5-15 mM Ammoniumformiat umfasst.
  9. Verfahren oder Verwendung nach Anspruch 8, wobei die Flussrate des isokratischen Lösungsmittels zwischen 0,1 und 1 ml/min, vorzugsweise zwischen 0,3 und 0,6 mg/min, liegt.
  10. Verfahren oder Verwendung nach einem der Ansprüche 1 bis 9, wobei der Schritt des Nachweises von geladenen Aerosolen bei einer Temperatur zwischen 30 und 100 °C, vorzugsweise zwischen 50 und 90 °C, durchgeführt wird.
  11. Verfahren oder Verwendung nach Anspruch 9, bei dem das Medium aus der Trennsäule mit überkritischem Fluid mit dem isokratischen Lösungsmittel gemischt und dann durch einen Splitter geleitet wird, wobei ein Teil der Mischung zu einem Massenspektrometer und ein anderer Teil zu einem Detektor für geladene Aerosole geleitet wird.
  12. Vorrichtung zur Durchführung des Verfahrens nach einem der Ansprüche 1 und 3 bis 11, wobei die Vorrichtung umfasst:
    - ein Chromatographiesystem mit überkritischem Fluid;
    - einen Detektor für geladene Aerosole;
    - einen Behälter, der ein überkritisches Fluid enthält;
    - optional einen Behälter, der das Co-Lösungsmittel des überkritischen Fluids enthält, und ein Mittel zum Mischen des überkritischen Fluids und des Co-Lösungsmittels;
    - ein Mittel zum Einspritzen des Kohlenwasserstoffgemisches in das Chromatographiesystem mit überkritischem Fluid;
    - einen Behälter, der das isokratische Lösungsmittel enthält;
    - ein Mittel zum Mischen des Mediums aus dem Chromatographiesystem mit überkritischem Fluid und des isokratischen Lösungsmittels;
    - optional ein Trennmittel;
    - optional ein Mittel zur Injektion einer Fraktion aus dem Separator in das Massenspektrometer.
EP19828249.3A 2018-12-17 2019-12-16 Verfahren zur auftrennung und gehaltsbestimmung von stoffen in einer mischung von kohlenwasserstoffen, entsprechende verwendung und vorrichtung Active EP3899525B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1873083A FR3090112B1 (fr) 2018-12-17 2018-12-17 Méthode de séparation et de quantification de composés dans un mélange d’hydrocarbures
PCT/EP2019/085329 WO2020127032A1 (fr) 2018-12-17 2019-12-16 Méthode de séparation et de quantification de composés dans un mélange d'hydrocarbures

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EP3899525A1 EP3899525A1 (de) 2021-10-27
EP3899525B1 true EP3899525B1 (de) 2024-04-17

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WO (1) WO2020127032A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112147251B (zh) * 2020-09-25 2022-04-08 安徽瑞思威尔科技有限公司 一种五味子酒中42种有效成分的UPC2-PDA-Q-Tof/MS检测方法

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US20040214341A1 (en) * 2003-04-25 2004-10-28 Fedorova Galina V. Analytical method for the detection and quantitation of fuel additives
WO2008127617A1 (en) * 2007-04-13 2008-10-23 Alltech Associates Inc. Method and apparatus for analyzing a sample such as a biodiesel fuel sample
US9702856B2 (en) * 2012-10-03 2017-07-11 Waters Technologies Corporation System and method for rapid analysis of polymer additives
US20170003264A1 (en) * 2014-01-24 2017-01-05 The University Of Wyoming Research Corporation D/B/A Western Research Institute Volatile Hydrocarbon Separation and Analysis Apparatus and Methods

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FR3090112A1 (fr) 2020-06-19
EP3899525A1 (de) 2021-10-27
WO2020127032A1 (fr) 2020-06-25
FR3090112B1 (fr) 2021-07-30

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